Well-dispersed palladium nanoparticles (Pd NPs) were prepared under the condition that trisodium citrate was the reduction agent and polyvinylpyrrolidone (PVP) was the stabilizing agent via sol-gel process. By making good use of the advanced electrospinning technology we obtained Pd NPs/PVP composite nanofibers films. Optical properties were examined by UV-visible absorbance spectra (UV-vis) and Fourier transform infrared spectroscopy (FTIR). The morphology and distribution of Pd NPs in/on PVP matrix were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). The results showed that Pd NPs presented as spherical spots and distributed in/on PVP nanofibers uniformly; their diameter was 4-10 nm and decreased with the increase of PVP. The as-prepared Pd NPs/PVP hybrid mats possess catalytic activity, stability and reusability, as verified by performance in Heck reaction.